Simple and efficient copper-catalyzed synthesis of symmetrical diaryl selenides from triarylbismuthanes and selenium under aerobic conditions

Article abstract of DOI:10.1016/j.jorganchem.2016.02.006

Symmetrical diaryl selenides were synthesized in moderate-to-excellent yields by Cu-catalyzed C(aryl)–Se bond formation followed by the reaction of triarylbismuthanes with elemental Se in the presence of Cu(OAc)₂ and 1,10-phenanthroline (10 mol%) under aerobic conditions. This reaction proceeded efficiently: All the aryl groups on Bi were transferred to the coupling products.

Full text of DOI:10.1016/j.jorganchem.2016.02.006

Accepted Manuscript
Simple and efficient copper-catalyzed synthesis of symmetrical diaryl selenides from
triarylbismuthanes and selenium under aerobic conditions
Mio Matsumura, Hanae Kumagai, Yuki Murata, Naoki Kakusawa, Shuji Yasuike
PII:
S0022-328X(16)30039-0
10.1016/j.jorganchem.2016.02.006
JOM 19390
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 17 November 2015
Revised Date: 27 January 2016
Accepted Date: 2 February 2016
Please cite this article as: M. Matsumura, H. Kumagai, Y. Murata, N. Kakusawa, S. Yasuike, Simple
and efficient copper-catalyzed synthesis of symmetrical diaryl selenides from triarylbismuthanes
and selenium under aerobic conditions, Journal of Organometallic Chemistry (2016), doi: 10.1016/
j.jorganchem.2016.02.006.
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Cu(OAc)2 (10 mol%)
1,10-Phen. (10 mol%)
Ar
Ar
Se
Bi Ar
+
Se
Ar
Ar
under Air

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Regular Paper
Simple and efficient copper-catalyzed synthesis of symmetrical diaryl selenides from
triarylbismuthanes and selenium under aerobic conditions
Mio Matsumura,a Hanae Kumagai,a Yuki Murata,a Naoki Kakusawa,b Shuji Yasuike a,*
a
School of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku,
Nagoya 464-8650, Japan
b
Faculty of Pharmaceutical Sciences, Hokuriku University, Ho-3 Kanagawa-machi, Kanazawa
920-1181, Japan
*Corresponding authors.
Address: School of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho,
Chikusa-ku, Nagoya 464-8650, Japan
Tel: +81-52-757-6774
E-mail address: s-yasuik@dpc.agu.ac.jp (S. Yasuike)
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ABSTRACT
Symmetrical diaryl selenides were synthesized in moderate-to-excellent yields by Cu-catalyzed
C(aryl)–Se bond formation followed by the reaction of triarylbismuthanes with elemental Se in the
presence of Cu(OAc)2 and 1,10-phenanthroline (10 mol%) under aerobic conditions. This reaction
proceeded efficiently: All the aryl groups on Bi were transferred to the coupling products.
Keywords:
Triarylbisumthane
Selenium
Diarylselenide
Copper catalyst
Se-arylation
Highlights:
Cu-catalyzed reaction of Se with Ar3Bi under aerobic conditions without an additive afforded
symmetrical diaryl selenides.
All the three aryl groups on Bi in Ar3Bi were transferred to the coupling products.
Symmetrical diaryl selenides were obtained from diverse Ar3Bi in good-to-excellent yields.
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1. Introduction
Organoselenium compounds are important reagents in organic synthesis and biology [1-8]. For
example, symmetrical diaryl selenides (Ar–Se–Ar) have attracted much attention in the last two
decades, because these exhibit wide biological activity such as antitumor and antioxidant activities
(Fig. 1.) [9-11]. The transition-metal-catalyzed C(aryl)–Se bond formation is one of the most
practical method in modern organic synthesis [3, 12-16]. Various metals including Pd, Ni, Fe and Cu
have been used to catalyze the reactions of aryl donors with a Se source. Cu-catalyzed cross-coupling
reactions are efficient for the synthesis of diaryl selenide [12-15]. Among these, the reactions of
diaryl diselenides with aryl halides [16-25] or boronic acids [26-32] were known as the synthesis of
symmetrical diaryl selenides. However, diaryl diselenides are not always commercially available and
require complicated preparation steps. Therefore, several methods have been reported for the
synthesis of symmetrical diaryl selenides using the following combination of aryl substrates with a
Se source: (1) aryl halides and Se [33-36], (2) aryl halides and potassium selenocyanate [37, 38], (3)
boronic acids and Se [39, 40], and (4) boronic acids and selenourea [41]. However, most of these
reactions require a base and/or an inorganic reagent as the additive. Recently, Yu and co-workers
reported the synthesis of symmetrical diaryl selenides by the cross-coupling of arylboronic acids
with Se powder without an additive in the presence of pyridine as a co-solvent under inert
atmosphere [40].
Fig. 1.
On the other hand, organobismuth compounds are usually nontoxic, environmentally benign, and
potentially useful as synthetic reagents [42-45]. Two methods for the synthesis of symmetrical diaryl
selenides using triarylbismuthanes (Ar3Bi) had been reported. Arnauld et al. reported the reaction of
an excess amount of Se powder (5 eq) with Ar3Bi at high temperature (170 °C) [46]. Recently,
Ogawa et al. have developed the photoinduced reaction of diphenyl diselenides with Ph3Bi affording
diphenyl selenides; however, an excess amount of the Bi agents bearing three aryl groups on Bi was
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required for the reaction [47]. Recently, we reported the Cu-catalyzed synthesis of unsymmetrical
diaryl sulfides and selenides (Ar–S–Arꞌ, and Ar–Se–Arꞌ) involving C(aryl)-S and C(aryl)-Se bond
formations by the reactions of diaryl disulfides (Arꞌ–S–S–Arꞌ) and diselenides (Arꞌ–Se–Se–Arꞌ) with
Ar3Bi under aerobic conditions [48, 49]. All the three aryl groups on the Bi reagent and both the
sulfanyl and selanyl groups of the diaryl disulfide and diselenide participated in this reaction. As a
continuation of our studies on C(aryl)-heteroatom bond formation, we now report an atom-economic
and simple Cu-catalyzed procedure for the synthesis of symmetrical diaryl selenides from Se powder
and Ar3Bi without the use of an additive under aerobic conditions.
2. Results and discussion
First, the optimal experimental conditions were determined for the cross-coupling of chalcogen
powder (S, Se, Te) with organobismuth and organoantimony compounds such as Ph3Bi (1a),
Ph3BiCl2 (2), Ph3BiF2 (3), Ph3Bi(OAc)2 (4), Ph3Sb (5), Ph3SbCl2 (6), Ph3SbF2 (7), and Ph3Sb(OAc)2
(8). Table 1 shows the results of the screening of chalcogens, aryl substrates, catalysts, ligands, and
solvents. The cross-coupling reactions of Ar3Bi with diaryl disulfides using CuOAc and
1,10-phenanthroline as the catalytic system under aerobic conditions in DMSO afforded the
corresponding unsymmetrical diaryl sulfides [48]. We first performed the reaction between
chalcogen powder with Ph3Bi (1a) under the optimal conditions reported by us previously [Cu(OAc)
(10 mol%), 1,10-phenanthroline (10 mol%), DMSO, 100 °C] (entries 1-3). The expected coupling
compound 9b was obtained in a high yield (81%) when Se was employed as the chalcogen (entry 2).
In this reaction, all the three phenyl groups on Bi participated in the C(Ar)–Se bond formation. On
the other hand, S and Te were less reactive toward this reaction (entries 1, 3). A complex mixture was
obtained in the reaction of 1a with Te. The reactions of Se with organobismuth compounds such as
1a, 2, 3 and 4 were performed under the same conditions to compare their reactivity (entries 2, 4-6).
The results show that Ph3Bi (1a) was the best aryl donor. When pentavalent compounds such as
Ph3BiCl2 (2) and Ph3Bi(OAc)2 (4) were employed in this reaction, diphenyl diselenide (10b) was
formed as the major product. When organoantimony reagents (5-8) were used instead of the Bi
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reagents, the reaction afforded 9b in <8% yield (entries 7-10). Next, several available Cu catalysts
were screened in the reaction of 1a with Se (entries 2, 11-18). Cu(OAc)2 was the best catalyst for this
reaction in terms of the yield (87%) of the expected product 9b and reaction time (3 h), and the yield
of byproduct 10b was < 1%. Various ligands (L1-6) were screened (entries 15, 20-24). The results
show that 1,10-phenanthroline (L1) was the most effective. The screening of solvents showed that
the reaction proceeded efficiently in DMSO (87%), DMF (84%), and CH3CN (60%), whereas
N-methylpyrrolidone, toluene, 1,4-dioxane, and 1,2-DCE were inefficient (entries 15, 26-31). A
significant decrease in the yield of product 9b under Ar atmosphere indicated that the presence of O2
in the reaction medium was essential for the progress of the reaction (entry 32). The progressive
addition of pure O2 shortened the reaction time (entry 33). The reactions under aerobic conditions
were simple and easy to operate. The reaction was sensitive to catalyst loading, as a decrease in the
loading of Cu(OAc)2 from 10 mol% to 5 mol% significantly reduced the yield of 9b (62%, 24 h,
entry 34). When the loading of Se (3 eq) was increased, this reaction afforded a mixture of 9b and
10b, and diphenyl diselenide (10b) was obtained as the major product (entry 35). Thus, the best
reaction condition was determined to be as follows: Ph3Bi (1a) was treated with 1.5 equiv. Se powder
using 10 mol% Cu(OAc)2 and 1,10-phenanthroline as the catalytic system in DMSO at 100 °C
without the use of any base and/or inorganic reagent under aerobic conditions.
Table 1
To demonstrate the efficiency and generality of the above-mentioned protocol, the reactions of
various Ar3Bi compounds (1a-l) and Se powder were investigated under the optimized reaction
conditions. The results are shown in Table 2. The yields of the coupling products are based on all the
three aryl groups on the Bi compounds used in the reaction. The reaction of Ar3Bi compounds (1b-i)
bearing electron-donating and electron-withdrawing substituents on the aromatic ring afforded the
corresponding symmetrical diaryl selenides (11-18) in good-to-excellent yields. The electronic nature
(electron-rich or electron-poor) of the substituents in the 4-substituted Ar3Bi did not affect the
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outcome of the reaction (entries 1-6). Sterically hindered ortho-substituted Bi compounds were also
coupled with Se, affording the corresponding diaryl selenides (16-19) even though a prolonged
reaction was required for the methyl-substituted series of Bi reagents (entries 7-10). Ar3Bi (1i)
bearing a CH2NH2 group in the ortho-position has a hypervalent bond between the N and Bi atoms
[50]. These hypervalent compounds showed a significant increase in the reactivity of the aryl group
toward the transition-metal-catalyzed cross-coupling reactions. For example, Tanaka et al. reported
that hypervalent Ar3Bi compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines,
are useful arylating agents for the synthesis of biaryl derivatives using Pd-catalyzed cross-coupling
reactions [51]. The reaction time of Ar3Bi (1i) bearing a CH2NH2 group in the ortho-position was
shorter than those of the methyl-substituted compounds 1g and 1h (entry 9). This reaction also
showed the effect of hypervalent compound. Moreover, the reactions of heterocyclic Bi reagents
afforded the corresponding selenides (20, 21) (entries 11, 12).
Table 2
To investigate the reaction mechanism, we have explored the possible reaction pathway. When the
reaction of Ph3Bi with elemental Se monitored by using GC, the generation of diphenyl diselenide
(10b) as well as diphenyl selenide (9b) was confirmed in the reaction process (Fig. 2.). The reaction
of Ph3Bi with diphenyl diselenide (10b) in the presence of Cu(OAc)2 (10 mol%) and
1,10-phenanthroline (10 mol%) under aerobic condition led to the formation of diphenyl selenide
(9b) in 89% yield. Therefore, a similar mechanism is possible as those proposed for the Chan-Lam
S-arylation with arylboronic acids by Yu [40], and Se-arylation of aryl iodides with Se by Jin [36],
and reaction of diaryl disulfides and diselenide with Ar3Bi by us [48, 49]. Fig. 3 shows the possible
mechanism for the synthesis of symmetrical diaryl selenides from Ar3Bi and Se. The first step of the
reaction involves the generation of a catalytically active (ꢀ-hydroxide)Cu(II) complex (A) from
CuOAc or Cu(OAc)2, 1,10-phenanthroline, molecular oxygen and moisture in air and/or solvent [52].
The transmetallation between Ar3Bi and A forms intermediate (B); subsequent oxidative addition of
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Se to B gives Cu(III) intermediate (C). The reductive elimination from C could affords desired aryl
selenide anion (Ar–Se-) and Cu(0). The aryl selenide anion is oxidized with H2O and aerobic oxygen,
affording diaryl diselenide (D). Cu(I) or (II) may be regenerated by air oxidation. Next, the
ligand-exchange reaction of regenerated A with the arylselanyl moiety of diaryl diselenide (D) forms
the intermediate (E); the subsequent oxidative addition of an aryl moiety of Ar3Bi to E affords
Cu(III) intermediate (F). The reductive elimination of coupling product (G) from intermediate (F)
regenerates the Cu catalyst. Another catalytic cycle may be possible: The transmetallation of A with
an aryl moiety of Ar3Bi affords B, and oxidative addition of the selanyl moiety of diaryl diselenide
(D) gives Cu(III) intermediate (F), which probably undergoes reductive elimination to afford the
asymmetric diaryl selenide.
Fig. 2 and 3.
3. Conclusion
Symmetrical diaryl selenides were synthesized from Se powder and Ar3Bi without an additive under
aerobic conditions. Under mild conditions, all the three aryl groups on the Bi reagent participated in
the reaction, and the reaction of bismuthanes bearing various functional groups afforded the
corresponding cross-coupling products in satisfactory yields. The studies on the mechanism of this
reaction and reactions of Ar3Bi with other coupling partners are underway.
4. Experimental
4.1. General
Melting points measurements were conducted on a Yanagimoto micro melting point hot-stage
1
apparatus (MP–S3) and reported as uncorrected values. H-NMR (TMS: δ: 0.00 as an internal
13
standard), C-NMR (CDCl3: δ: 77.00 as an internal standard) and spectra were recorded on JEOL
JNM–AL400 (400 MHz and 100 MHz respectively) spectrometers in CDCl3. Mass spectra were
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obtained on a JEOL JMP-DX300 instrument (70 eV, 300 ꢀA). All chromatographic separations were
accomplished with Silica Gel 60N (Kanto Chemical Co., Inc.). Thin-layer chromatography (TLC)
was performed with Macherey-Nagel Pre-coated TLC plates Sil G25 UV254. Terminal alkynes 9 were
purchased from Wako Pure Chemical Industries Ltd. and TCI Fine Chemicals, Japan.
Triphenylbismuthane (1a) and tris(o-tolyl)bismuthane (1g) were purchased from TCI Fine Chemicals,
Japan, and other triarylbismuthanes such as 1b-d [53], 1e [54], 1f [46], 1h [55], 1i [50], 1j [53], 1k
[56] and 1l [49] were prepared according to the reported procedures.
4.2. Reaction of Ar3Bi with Se
A mixture of Ar3Bi 1 (0.5 mmol), Se powder (0.75 mmol), Cu(OAc)2 (0.05 mmol), and
1,10-phenanthroline (0.05 mmol) in DMSO (5 mL) was heated at 100 °C under air atmosphere for
the desired time (Table 2) until the complete consumption of the starting material on TLC. After
diluting with CH2Cl2 (50 mL) and water (30 mL), the reaction mixture was separated and the
aqueous layer was extracted with CH2Cl2 (30 x 2 mL). The combined organic layer was washed with
5% aqueous ammonia and water, dried over anhydrous MgSO4 and concentrated under reduced
pressure. The residue was purified by column chromatography on silica gel using a mixture of
hexane/CH2Cl2 as the eluent, affording diaryl selenides 9b and 11-20. Compound (21) was purified
by column chromatography on aluminum oxide with hexane/Et2O. The products 9b and 11-20 were
confirmed by comparison of their NMR data and mass spectra with the literature data.
1
Diphenyl selenide (9b) [31, 35]: Pale yellow oil. H NMR (400 MHz, CDCl3) δ: 7.20-7.28 (6H, m,
Ar-H), 7.40-7.49 (4H, m, Ar-H); 13C NMR (100 MHz, CDCl3) δ: 127.1, 129.2, 131.3, 132.8. LR-MS
m/z: 234 (M+).
Bis(4-methoxyphenyl) selenide (11) [31, 35]: Colorless prisms. mp 55-57 ˚C (from hexane). 1H NMR
(400 MHz, CDCl3) δ: 3.77 (6H, s, OCH3), 6.80 (4H, d, J = 8.8 Hz, Ar-H), 7.39 (4H, d, J = 8.8 Hz,
Ar-H); 13C NMR (100 MHz, CDCl3) δ: 55.2, 114.9, 122.0, 134.5, 159.2. LR-MS m/z: 294 (M+).
1
Bis(p-tolyl) selenide (12) [31, 35]: Colorless prisms. mp 68-70 ˚C (from hexane). H NMR (400
MHz, CDCl3) δ: 2.32 (6H, s, CH3), 7.07 (4H, d, J = 7.8 Hz, Ar-H), 7.35 (4H, d, J = 7.8 Hz, Ar-H);
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13C NMR (100 MHz, CDCl3) δ: 21.1, 127.7, 130.1, 133.0, 137.2. LR-MS m/z: 262 (M+).
1
Bis(4-chlorophenyl) selenide (13) [35]: Colorless flakes. mp 95-97 ˚C (from hexane - CH2Cl2). H
13
NMR (400 MHz, CDCl3) δ: 7.24 (4H, d, J = 8.3 Hz, Ar-H), 7.37 (4H, d, J = 8.3 Hz, Ar-H); C
NMR (100 MHz, CDCl3) δ: 129.0, 129.6, 133.9, 134.3. LR-MS m/z: 302 (M+).
1
Bis(4-ethoxycarbonylphenyl) selenide (14) [57]: Colorless prisms. mp 38-41 ˚C (from hexane). H
NMR (400 MHz, CDCl3) δ: 1.39 (6H, t, J = 7.1 Hz, CH3), 4.38 (4H, t, J = 7.1 Hz, CH2), 7.50 (4H, d,
J = 8.3 Hz, Ar-H), 7.94 (4H, d, J = 8.3 Hz, Ar-H); 13C NMR (100 MHz, CDCl3) δ: 14.3, 61.1, 129.7,
130.4, 132.5, 136.7, 166.1. IR (KBr) cm-1: 1712. LR-MS m/z: 378 (M+).
1
Bis(4-trifluoromethylphenyl) selenide (15) [35]: Colorless oil. H NMR (400 MHz, CDCl3) δ: 7.54
(4H, d, J = 9.3 Hz, Ar-H), 7.57 (4H, d, J = 9.3 Hz, Ar-H); 13C NMR (100 MHz, CDCl3) δ: 123.9 (q,
Jc, f = 272 Hz), 126.3 (q, Jc, f = 3.9 Hz), 130.0 (q, Jc, f = 32.3 Hz), 133.1, 135.2. LR-MS m/z: 370 (M+).
1
Bis(o-tolyl) selenide (16) [35]: Colorless flakes. mp 57-60 ˚C (from hexane). H NMR (400 MHz,
CDCl3) δ: 2.39 (6H, s, CH3), 7.04 (2H, t, J = 7.4 Hz, Ar-H), 7.16-7.24 (6H, m, Ar-H); 13C NMR (100
MHz, CDCl3) δ: 22.2, 126.8, 127.6, 130.2, 131.3, 133.2, 139.8. LR-MS m/z: 262 (M+).
Bis(2,4,6-mesityl) selenide (17) [57]: Colorless prisms. mp 104-105 ˚C (from hexane). 1H NMR (400
13
MHz, CDCl3) δ: 2.23 (6H, s, CH3), 2.24 (12H, s, CH3), 6.83 (4H, s, Ar-H); C NMR (100 MHz,
CDCl3) δ: 20.8, 23.5, 128.9, 129.4, 136.9, 141.3. LR-MS m/z: 318 (M+).
Bis[2-(N, N-dimethylamino)benzyl] selenide (18) [58]: Colorless prisms. mp 63-65 ˚C (from hexane).
1H NMR (400 MHz, CDCl3) δ: 2.25 (12H, s, CH3), 3.56 (4H, s, CH2), 7.08 (2H, dt, J = 7.8, 1.5 Hz,
Ar-H), 7.22 (2H, dt, J = 7.8, 1.5 Hz, Ar-H), 7.26 (2H, dd, J = 7.8, 1.5 Hz, Ar-H), 7.39 (2H, d, J = 7.8
13
Hz, Ar-H); C NMR (100 MHz, CDCl3) δ: 44.9, 63.9, 127.0, 127.8, 129.8, 134.2, 134.4, 140.3.
LR-MS m/z: 348 (M+).
Bis(1-naphthyl) selenide (19) [31, 35]: Colorless prisms. mp 103-105 ˚C (from hexane - CH2Cl2). 1H
NMR (400 MHz, CDCl3) δ: 7.27 (2H, t, J = 7.3 Hz, Ar-H), 7.48 (2H, dd, J = 7.3, 1.5 Hz, Ar-H),
7.50-7.54 (4H, m, Ar-H), 7.78 (2H, d, J = 8.3 Hz, Ar-H), 7.83-7.88 (2H, m, Ar-H), 8.32-8.36 (2H, m,
Ar-H); 13C NMR (100 MHz, CDCl3) δ: 126.1, 126.3, 126.8, 127.1, 128.4, 128.6, 129.8, 137.2, 133.6,
134.1. LR-MS m/z: 334 (M+).
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Bis(2-thienyl) selenide (20) [41]: Colorless oil. 1H NMR (400 MHz, CDCl3) δ: 6.95 (2H, dd, J = 3.4,
5.4 Hz, Ar-H), 7.27 (2H, d, J = 3.4 Hz, Ar-H), 7.35 (2H, d, J = 5.4 Hz, Ar-H); 13C NMR (100 MHz,
CDCl3) δ: 126.3, 127.9, 130.9, 134.7. LR-MS m/z: 246 (M+).
Bis(2-benzothienyl) selenide (21): Yellow prisms. mp 129-131 ˚C (from hexane - CH2Cl2). 1H NMR
(400 MHz, CDCl3) δ: 7.28 (2H, dt, J = 7.3, 1.5 Hz, Ar-H), 7.32 (2H, dt, J = 7.3, 1.5 Hz, Ar-H), 7.53
13
(2H, s, Ar-H), 7.73 (4H, dt, J = 7.3, 1.5 Hz, Ar-H); C NMR (100 MHz, CDCl3) δ: 121.8, 123.4,
124.5, 124.8, 127.6, 131.0, 139.9, 143.4. LR-MS m/z: 346 (M+).
Acknowledgments
Partial financial support for this work was provided by a Grant-in Aid for Scientific Research from
the Ministry Education, Sciences, Sports and Culture of Japan. This research was also supported by a
research grant from Institute of Pharmaceutical Life Sciences, Aichi Gakuin University and
Hokuriku University.
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13

a
ACCEPTED MANUSCRIPT
Table 1. Cu-catalyzed reaction of organobismuth and antimony compounds 1-8 with chalcogen elements Y.
Yield (%)
Time
(h)
24
5
Entry
Substrate Y (S, Se, Te) Cu cat.
ligand
Solvent
9b
10b
1
2
3
4
5
6
7
8
1a
1a
1a
2
3
4
5
6
7
8
S
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuOAc
CuI
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
---
L2
L3
L4
L5
L6
---
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
9a: 36
9b: 81
9c: <1
9b: 31
9b:
9b: 35
9b:
9b: ND
9b: ND
9b:
9b: 82
10a: 21
Se
Te
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
Se
10b: <1
10c: <1
10b: 62
6
24
24
24
24
24
24
24
24
24
24
24
3
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
2
3
10b:
5
10b: 46
10b: ND
10b: ND
10b: ND
3
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32d
33e
34f
35g
8
10b:
5
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
10b: <1
10b: <1
10b: <1
CuBr
CuCl
CuO
Cu(OAc)2
CuBr2
CuCl2
CuO2
---
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
9b: 77
9b: 75
9b: 67
10b:
4
9b: 87 (85)c
9b: 79
10b: <1
10b: ND
10b: <1
10b: 45
10b: 18
10b: <1
9b: 75
9b:
8
9b: ND
9b: 84
9b: 76
9b: 77
9b: 70
9b: 75
9b: 62
9b: 82
9b: 60
9b: 27
9b:
9b:
9b:
9b: 49
9b: 80
9b: 62
9b: 17
10b:
10b:
10b:
10b:
10b:
10b: <1
10b: 16
10b:
10b: 40
10b: 35
10b: 26
10b:
10b: <1
2
3
5
7
5
CH3CN
NMP
5
Toluene
1,4-dioxane
1,2-DCE
DMSO
DMSO
DMSO
DMSO
9
8
8
8
24
4
10b:
3
10b: 51
a Condition: 1a-8 (0.5 mmol), chalcogen element (0.75 mmol), Cu cat (0.05 mmol), ligand (0.05 mmol).
b
GC yield using dibenzyl as internal standard. The yield 100% corresponds to the formation of 0.75 mmol of 9 and 0.375
mmol of 10.
c Isolated yield.
d Under Ar.
e Under O2
f Cu cat (5 mol%).
g Selenium (1.5 mmol)

ACCEPTED MANUSCRIPT
Table 2. Cu-catalyzed procedure for the synthesis of symmetrical diaryl selenides from triarylbismuthane 1 and selenium
powder a
Entry
1
Ar3Bi
Ar
Time (h)b
3
Product
Yield (%)c
1b
11: 87
2
3
4
5
6
1c
1a
1d
1e
1f
3
3
3
3
2
12: 85
9b: 85
13: 87
14: 84
15: 90
7
8
9
1g
1h
1i
24
24
5
16: 87
17: 76
18: 73
Me
Me
Me
10
3
19: 72
1j
11
12
1
1
20: 73
21: 77
1k
1l
a 1 (0.5 mmol), Se (0.75 mmol), Cu(OAc)2 (0.05 mmol), 1,10-phenanthroline (0.05 mmol).
b Heating of the reaction mixture was terminated with extinction of 1 on TLC.
c Isolated yield. The yield 100% corresponds to the involvement of three aryl groups on 1.

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Fig. 2. Reaction of triphenylbismuthane 1a with selenium

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